Method foe converting higher-boiling petroleum hydrocarbons into



G. W. GRAY.

ME HOD FOR CONVERTING HIGHER BOILING PETROLEUM HYDROCARBONS INTO LOWER BOILING PETROLEUM HYDROCARBONS.

APPLICATION FILED IAN. 23,1913.

' Patented Aug. 8, 1916.

LEQSEQL IIIII! vvitmaooao WNETED @TATES m:

GEORGE WILLIAM GRAY, OF HOUSTON, TEXAS.

METHOD FOR CONVERTING HIGHER-BOILING PETROLEUM HYDROCARBO'NS INTO LOWER-BOILING PETROLEUM HYDROCARBONS.

Specification of Letters Patent.

Patented Aug. 8, 1916.

Application filed January 23, 1913. Serial No. 743,714.

To all whom it may concern Be it known that I, Gnonon WILLIAM GRAY, a citizen of the United States, residing at Houston, in the county of Harris and State of Texas, have invented certain new and useful Improvements in Methods for Converting Higher-Boiling Petroleum Hydrocarbons into Lower-Boiling .Petroleum Hydrocarbons, of which the following is a specification.

My invention consistslof novel processes of converting higher-boiling petroleum hydrocarbons of complex molecules into lowerboiling petroleum hydrocarbons of simpler molecules. i

In an application for a patent filed by me on even date herewith bearing Serial No. 743,713, I have described novel processes for converting highei boiling hydrocarbons into lower-boiling hydrocarbons.

My present invention is a modification of said processes, by means of which I am able to use higher and less carefully regulated temperatures than there described, while 0btaining separately naphtha or gasolene'; and, while using said higher temperatures, may convert substantially all the higher-boiling hydrocarbons into naphtha or gasolene; or, if preferred, may convert the same into naphtha and illuminating oil obtained separately.

of individuals having different boiling points. in makmg a distillation test on a sampleof naphtha or gasolene, for example, a quantity is introduced into a flask provided with a thermometer, .the outlet of the flask being connected to a condenser. Heat is gradually applied. The ten'lperature at which the first liquid drops into the re ceiving flask is called the initial boiling point. From time to time when the flow of liquid ceases, the temperature 1s slightly raised. The temperature at which no oil. is left in the flask is called the end boiling oint. Gasolene or naphtha is a product which will begin to distil anywhere from about 70 to 150 F., and will all distil 'ofi below a temperature of about 350 to 4009 F; while illuminating oil is a product which will begin to distil anywhere from changed and is subject to change in the future, no more definite term can be .used and no more definite figures can be given. For example, it 1s a matter of common knowledge that as the demand for naphtha 0r gasolene has increased much more rapidly than the demand for illuminating oil and as improvements have adapted gas engines to utilize heavier grades of gasolene, the end boiling point of commercial gasolene has progressively risen, and the initial boiling point of commercial illuminating oil has correspondingly risen.

\Vhatever may be the end-boiling-point of commercial naphtha or of illuminating oil, the principle remains the samethat is to say, if the temperature of the vapor given off is maintained not above 325 F., substantially the whole body of the higherboiling-point hydrocarbons may be, if desired,- converted into hydrocarbons having boiling points not above that temperature; and it the temperature is maintained not above 350 E, substantially the whole body may be. if desired. converted into hydrocarbons having boiling-points not above that.

temperature. The same principle exactly would apply it, in the future, commercial naphtha should include constituents having boiling-points as high as 400 F., or higher. In the accompanying drawings I have shown one form of still which is suitable for J is the vapor exhaust pipe and K is an inlet pipe for oil and chemicals. The pipe J leads to a chamber N from which a vapor pipe 0 leads to the condenser. This chamber N represents diagrammatically one or more cooling chambers of any suitable construc tion (various ditllerent constructions being now well. known).

[is an example. I may take 100 partsot petroleum distillate freed from naphtha products-such as gas oil made from a par allin or semi-parall'in or semi-asphalt crude oiland add to it 5 parts of a suitable agent-such as anhydrous aluminum chlorid for example. The mixture is then heated to a temperature above the end boiling-point of naphtha. As explained in my said appli cation, so long as the hydrocarbons in the still are not heated to produce a vapor substantially above the cndboiling-point ot' mu)htlmsay about 400 degrees l .the

' vapors driven (ill will contain little or no illuminating oil. or hydroearbons of. higher boiling-point than naphtha; but. when the temperature is Increased substantially above that point. illumimitine oil'will be driven otl', and this will be condensed in the cooling chamber, or chambers. diagrammatically indicated by N in the. drawings, so that only naphtha or gasolene will pass to the condensing chamber. ll it is desired to convert ture employed above the en l-bo1hng-po1nt ot' naphtha. the larger will be the percentage yield of illuminating oil and the smaller will be the percentage yield of naphtha. It a temperature much higher than the end-boiling-point ol illuminating oil be employed in the still. the agent will be driven ofl", rcsuiting; not only in th e loss of that agent, but also in clogging the pipes. l p

The still is prelcrably ,provided with stirring apparatus of any lcnown and approved 'lorm-such as the blades 3*), E and the chains l, shown in tlie drawingst0 keep th 2 aluminum chlorid in suspension and in intimate contact with the oil and to prevent overheating it. Preferably also fresh charges of oil are added from time to time through the inlet K to avoid distilling the contents to dryness and to obta n the advantage of the repeated use of the agent, the eliiciency of which appears to persist for a considerable time. It the charge were distilled to dryness. the agcnt would be lost, coke would be formed and cleaning the still after each charge would be required.

It desirable, additional aluminun'i chlorid may be added from time to time as required. The use of a larger percentage of anhydrous aluminum chlorid than that named in the above examplesay 10 parts to 100- parts of oil, for example causes the desired reactions to take place much more rapidly.

Other equivalent agents may be used in combination with, or in place of, anhydrous aluminum chlorid-such, for example, as anhydrous ferric chlorid and perhaps other substances which, up to his time, I have not had time to try. The use of equivalent agents is included within the scope of my claims. i have tountl anhydrous ferric chlorid to be a less activeagent than anhydrous aluminum chlorid, and that it is necessary to uselarger quantities of it to etl'ect the same result.

The process above described may also be practised with illuminating oil or lubricating oil as starting materials. It may also be practised with crude oils as the starting material, but it is less advantageous to use crude oil because of its contained impurities.

hat I claim and desire to secure by Letters Patent of the United States, is

1. The process of converting hydrocarbons having higher-boiling-points into hydrocarbons having lower-boiling-points, which consists in heating such hydrocarbons in the presence of anhydrous aluminum chlorid to a temperature producingvapor having a temperature above the end-boilingpoint of naphtha, but below the end-boilingpoint of illuminating oil, maintaining such vapor temperature to separate the oil as naphtha and illuminating oil, condensing the illuminating oil driven off in a prelimi nary cooling chamber, and conducting the. naphtha driven ofl to a condenser.

2. The process of converting hydrocarbons having higher-boiling-points into naphtha, which consists in heating said hydrocarbons in the presence of anhydrous aluminum chlorid to a temperature producing vaporhaving a temperature above the end-boiling-point of naphtha, but below the end-boiling-point of illuminating oil, condensing the illuminating oil driven off in a preliminary cooling chamber, returning said oil to the still to be further acted on whereby higher-boiling oil is converted into naphtha, and conducting the naphtha driven olt' to a condenser.

23. The process of convertlng hydrocarbons having liiglier-boiling-points into hyvapor temperature until the greater part.

of the oil has been separated as'naphtha and illuminating oil, condensing the illuminating oil driven ofl" in a preliminary coolingchamber, and conducting the naphtha driven 5 ofi to a condenser.

4. The process of converting hydrocarbons having higher-boiling-points into naphtha, which consists in heating said hydrocarbons in the presence of anhydrous '10 aluminum chlorid to a temperature producing vapor having a temperature above the end-boiling-point of'naphtha, but below the end-b0i'ling-p0int.0f illuminating oil, condensing the illuminating oil driven 01f in a preliminary cooling chamber, returning said oil to the still to be further acted on, whereby the greater portion of the higherboiling oil is converted into naphtha, and conducting the naphtha driven off to'a condenser. I

'In testimony whereof I have hereunto signed my name in the presence of two subscribing witnesses. p

GEORGE WILLIAM GRAY.

Witnesses:

M. E. MCNINCH, J. Enemy BULL. 

